JPH0571939B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to color photographic materials, particularly to prevention of fading and discoloration of dye images finally obtained by developing color photographic materials, and particularly to spirobenzofuran-based antifading agents. It is something. (Prior Art) Color images obtained by photographically processing silver halide color photographic materials are generally azomethine dyes or indoaniline dyes formed by the reaction of an oxide of an aromatic primary amine developing agent with a coupler. Consists of. The color photographic images obtained in this way are not necessarily stable against light or moist heat, and if exposed to light for a long period of time or stored under high temperature and high humidity, the dye image may fade or discolor. This causes deterioration of image quality. Such fading of the image is a fatal drawback to the recording material. As methods to eliminate these defects, proposals have been made to select and use couplers with low fading properties, to use anti-fading agents to prevent fading due to light, and to use ultraviolet absorbers to prevent image deterioration due to ultraviolet rays. ing. Among these, anti-fading agents have a great effect in preventing image deterioration; for example, hydroquinones, hindered phenols, hindered amines, chromans, coumarans, aminophenols, and the phenolic hydroxyl groups of these compounds are silylated, acylated, Alkylated ethers or esters, as well as metal complexes (U.S. Pat. Nos. 3935016, 3982944, 4254216, 3700455,
British Patent No. 2066975, U.S. Patent No. 3336135, U.S. Patent No. 4268593, U.S. Patent No. 3462300, U.S. Patent No. 3574627,
No. 3573050, No. 4155765, Special Publication No. 1973-
12337, U.S. Patent No. 4050938, U.S. Patent No. 4241155,
JP-A-60-97353) is known. Although these compounds have been recognized to be effective as agents for preventing fading and discoloration of dye images, they are insufficient to meet the demands of customers who are increasingly demanding high image quality, and they do not change the hue. However, it has not been able to exhibit an overall excellent effect for color photography because it causes fog, poor dispersion, and microcrystals after emulsion coating. On the other hand, antifading agents with a spiro ring have attracted attention due to their unique structure and high antifading performance, and Spirochroman (U.S. Patent No. 3764337)
Spiroindane (U.S. Patent No. 4360589, U.S. Patent No. 4416978, British Patent No. 4174220);
No. 2135788A, JP-A-57-204035, JP-A No. 57-
204037 and 61-6652). Although these methods all have the effect of preventing fading, they are still insufficient as technology advances rapidly with the changing times, and demands for stronger images have become stronger. (Problems to be Solved by the Invention) The purpose of the present invention is to prevent color images from discoloring for a long period of time.
An object of the present invention is to provide a color photographic material having a high degree of storage stability and in which yellow staining on a white background is significantly suppressed. Another object of the present invention is to provide a photographic discoloration prevention method that is sufficiently effective in preventing fading and discoloration of color images without causing changes in hue or fogging, and that does not produce microcrystals after being applied. The aim is to provide agents for Another object of the present invention is to produce color photographs that have excellent solubility in high-boiling point solvents, do not form microcrystals before or after coating, and do not adversely affect other photographic additives. An object of the present invention is to provide an anti-fading agent for use. (Means for Solving the Problems) As a result of various studies on compounds having a spiro ring structure, the present inventors incorporated at least one compound represented by the following general formula [I] into a silver halide color photographic light-sensitive material. It has been revealed that the object of the present invention can be achieved by containing the above. General formula [I]

[Formula] (In the formula, R and R′ may be the same or different,
hydrogen atom, alkyl group, alkenyl group, respectively.
Aryl group, heterocyclic group, R ₁₁ CO−, R ₁₂ SO ₂ −,
R ₁₃ NHCO- or a silyl group. here
R ₁₁ , R ₁₂ and R ₁₃ each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group,
It represents an alkenoxy group, an aryloxy group, an alkylthio group, an alkenylthio group, an arylthio group, an alkoxycarbonyl group, an alkylcarbonyl group, a hydroxy group, an alkylcarbonyloxy group, a carbamoyl group, or an acylamino group.
R ₇ , R ₈ , R ₉ and R ₁₀ may be the same or different and each represents a hydrogen atom or an alkyl group.
However, among R, R ₁ to _{R 3} , R', and R ₄ to _{R 6} , the groups at mutually ortho positions do not combine to form a ring. ) The substituent represented by general formula [I] will be explained in more detail. In the formula, R and R' may be the same or different,
hydrogen atom, alkyl group (e.g. methyl,
ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl), alkenyl groups (e.g. allyl, octenyl, oleyl), aryl groups (e.g. phenyl, naphthyl), heterocyclic groups (e.g. tetrahydropyranyl, pyrimidyl) ) or a group represented by R ₁₁ CO, R ₁₂ SO ₂ or R ₁₃ NHCO. Here, R ₁₁ , R ₁₂ , and R ₁₃ each represent an alkyl group (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl,
tert-octyl, benzyl), an alkenyl group (eg allyl, octenyl, oleyl), an aryl group (eg phenyl, methoxyphenyl, naphthyl) or a heterocyclic group (eg pyridyl, pyridimidyl). R and R' further represent a silyl group (eg trimethylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, triphenylsilyl). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine), an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl),
Alkenyl groups (e.g. allyl, hexenyl, octenyl), alkoxy groups (e.g. methoxy,
ethoxy, benzyloxy), alkenoxy groups (e.g. 2-propenyloxy, hexenyloxy), aryloxy groups (e.g. phenyloxy, naphthyloxy), alkylthio groups (e.g.
methylthio, butylthio), alkenylthio groups (e.g. 2-butynylthio, 2-pentenylthio), arylthio groups (e.g. phenylthio,
naphthylthio), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl),
Alkylcarbonyl groups (e.g. acetyl, tetradecanoyl), hydroxy groups, alkylcarbonyloxy groups (e.g. acetyloxy, tetradecanoyloxy), carbamoyl groups (e.g.
N-methylcarbamoyl, N-methyl-N-dodecylcarbamoyl), or an acylamino group (eg, acetylamino, benzamino). R ₇ , R ₈ , R ₉ and R ₁₀ may be the same or different and each represents a hydrogen atom or an alkyl group (eg, methyl, ethyl, n-butyl). Among the compounds represented by the general formula [I] of the present invention, from the viewpoint of the effects of the present invention, it is preferable that R ₇ , R ₈ , R ₉ , and R ₁₀ are all hydrogen atoms, particularly R,
Preferably, R' consists of a combination of a hydrogen atom and an alkyl atom. When the compound represented by the general formula [I] of the present invention is used in combination with the above-mentioned known antifading agent, the effect is even greater. Similarly, two or more compounds represented by the general formula [I] may be used in combination. The compound of general formula [I] used in the present invention differs depending on the type of coupler, but usually
Suitably, it is used in a range of 0.5 to 200 weight percent, preferably 2 to 150 weight percent. Representative examples of these compounds are shown below.
This does not limit the compounds used in the present invention.

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[ka]

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[Chemical formula] Next, 3 represented by the general formula [I] of the present invention,
A method for producing 3′(2H,2′H)-spirobibenzofuran derivatives is shown. 3 represented by general formula [I],
The 3'(2H,2'H)-spirobibenzofuran derivative is produced by the following synthetic process and analogous thereto. Synthesis process formula

[ka]

[Formula] Here, R, R', R ₇ , R ₈ , R ₉ and R ₁₀ have the same meanings as above. _R0 represents a substituent defined by _R1 to _R6 , and n represents an integer of 0 to 3. The compound of general formula [I] is reacted with p-alkoxyphenol analogs 1 to 1 and 1,3-dihalogen-2-propane derivatives to produce compounds 2 to 1. By intramolecular ring closure of this, 3,3′(2H,
2′H)-spirobibenzofuran derivatives 3 to 3 can be produced. Synthesis examples of typical compounds are shown below. Synthesis of 5,5'-dimethoxy-3,3'(2H,2'H)-spirobibenzofuran (exemplified compound (3)) 100 ml of methylene chloride was added to 37.2 g (0.30 mol) of p-methoxyphenol, and ,3
19 g (0.15 mol) of -dichloro-2-propanone was added and dissolved, and the mixture was stirred at 0°C to 5°C. To this, 9 ml of concentrated sulfuric acid was added dropwise over 1 hour, and the mixture was further stirred for 2 hours. This reaction mixture was poured into 200 ml of ice water, and extracted with 200 ml of methylene chloride. 300ml
After washing twice with cold water, it was dried with calcium chloride. After filtering off calcium chloride, methylene chloride was distilled off under reduced pressure, and the resulting oil was quickly subjected to column chromatography to remove unreacted raw materials. 100 ml of benzene was added to the remaining oil and stirred at 15°C to 20°C. 2g of sodium hydride here
(0.083 mol) was added gradually. After further stirring for 1 hour, the mixture was cooled to 0°C to 10°C, and 20ml of methanol was added dropwise over 10 minutes while stirring. The reaction mixture was poured into 200 ml of ice water containing 7 ml of concentrated hydrochloric acid. Extract with 100ml of vinegar and 200ml of cold water.
After washing twice, it was dried with anhydrous sodium sulfate. After filtering out Glauber's salt, ethyl acetate was distilled off under reduced pressure, and the resulting oil was purified by column chromatography. Add 40 ml of methanol to the obtained material, crystallize it, and add 40 ml of methanol.
Recrystallization was performed to obtain 9.4 g of Exemplified Compound (3). Yield 22% mp179℃～180℃ Elemental analysis (C ₁₇ H ₁₆ O ₄ ) Measured value C: 71.78% H: 5.64% Calculated value C: 71.82% H: 5.67% 5,5'-dimethoxy-6,6' -dimethyl-3,
Synthesis of 3'(2H,2'H)-spirobibenzofuran (exemplified compound (7)) 27.6 g of 3-methyl-4-methoxyphenol
(0.20 mol), add 100 ml of methylene chloride,
Additionally, 12.7 g of 1,3-dichloro-2-propane
(0.10 mol) was added and dissolved, and the mixture was stirred at 0°C to 5°C. 6 ml of concentrated sulfuric acid was added dropwise to this over 1 hour, and the mixture was further stirred for 2 hours. Pour this reaction mixture into 200 ml of ice water.
ml and extracted by adding 100 ml of methylene chloride. After washing twice with 200 ml of cold water, it was dried with calcium chloride. After filtering off calcium chloride, methylene chloride was distilled off under reduced pressure, and the resulting oil was quickly subjected to column chromatography to remove unreacted raw materials. 70 ml of benzene was added to the remaining oil and stirred at 10°C to 15°C. 1.5 g (0.063 mol) of calcium hydride was gradually added thereto. After further stirring for 1 hour, the mixture was cooled to 0°C to 10°C, and while stirring, 20ml of methanol was added dropwise over 10 minutes. This reaction mixture was diluted with ice water containing 5 ml of concentrated hydrochloric acid.
Pour into 200ml. Extract with 100ml of vinegar and 200ml
After washing twice with cold water, it was dried with anhydrous sodium sulfate.
After filtering out Glauber's salt, ethyl acetate was distilled off under reduced pressure, and the resulting oil was purified by column chromatography. The obtained product was crystallized by adding 20 ml of methanol, and further recrystallized from 30 ml of methanol to obtain 5.9 g of Exemplified Compound (7). Yield 19% mp79℃~80℃ Elemental analysis (C ₁₉ H ₂₀ O ₄ ) Measured value C: 73.11% H: 6.47% Calculated value C: 73.06% H: 6.45% Represented by general formula [I] of the present invention The compounds can be used in combination with yellow, magenta, or cyan couplers. The couplers used in combination may have an amount of 4 equivalents or 2 equivalents relative to silver ions, and may also be in the form of polymers or oligomers. Further, the couplers used in combination may be used alone or in a mixture of two or more types. The general formulas of preferred couplers for use in the present invention are shown below. General formula ()

【formula】 General formula ()

【formula】 General formula ()

【formula】 General formula ()

【formula】 General formula ()

[Formula] (wherein R ₁ , R ₄ and R ₅ are each an aliphatic group,
represents an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ₂ represents an aliphatic group, R ₃
and R ₆ are hydrogen atom, halogen atom,
represents an aliphatic group, an aliphatic oxy group, or an acylamino group, R ₇ and R ₉ represent a substituted or unsubstituted phenyl group, and R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or represents an aromatic sulfonyl group, R ₁₀ represents a hydrogen atom or a substituent, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and Zb are methine, substituted methine, or =
It represents N-, and Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent (hereinafter abbreviated as a leaving group). R ₂ in general formula () and general formula ()
and R ₃ and R ₅ and R ₆ may each form a 5-, 6-, or 7-membered ring. Furthermore, R ₁ , R ₂ , R ₃ or Y ₁ ; R ₄ , R ₅ , R ₆ or
_Y2 ; _R7 , _R8 , _R9 or _Y3 ; _R10 , Za, Zb or _Y4 ;
Q or Y ₅ may form a dimer or more multimer. The aliphatic group mentioned here refers to a linear, branched or cyclic alkyl, alkenyl or alkynyl group. Preferred specific examples of couplers represented by general formulas () and () are shown below.

【table】

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[Table] Preferred specific examples of couplers represented by general formulas () and () are shown below.

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[Table] Preferred specific examples of couplers represented by the general formula () are shown below.

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[Table] Literatures describing other exemplary compounds or synthesis methods of couplers represented by the general formulas () to () are listed. Cyan couplers represented by general formula () and general formula () can be synthesized using known methods. For example, the cyan coupler represented by the general formula () is synthesized by the method described in US Pat. Nos. 2,423,730 and 3,772,002. Cyan couplers represented by the general formula () are disclosed in U.S. Patent Nos. 2895826 and 4333999,
It is synthesized by the method described in No. 4327173. The magenta coupler represented by the general formula () is
No. 48-27930, No. 53-33846 and U.S. Pat.
It is synthesized by the method described in No. 3519429. The magenta coupler represented by the general formula (
It is synthesized by the method described in JP-A-59-171956 and JP-A-60-33552. The yellow coupler represented by the general formula () can be synthesized by the methods described in JP-A-54-48541, JP-B-58-10739, US Pat. No. 4,326,024, Research Disclosure No. 18053, and the like. The couplers used in the present invention are also colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DIR).
coupler). The coupler may be one in which the product of the coupling reaction is colorless. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 44
-32461, JP-A-51-26034 specification, JP-A-52-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British patents
953454, JP-A No. 52-69624, JP-A No. 49-122335,
Those described in Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, US Pat. No. 3,297,445, US Pat.
No., West German Patent Application (OLS) No. 2417914, Japanese Patent Publication No. 1983
-15271 and those described in JP-A-53-9116 can be used. Among these, use in combination with magenta couplers represented by general formulas () and (V) is particularly preferred in terms of the effects of the present invention. These couplers are generally added in an amount of 2 x 10 ^-3 mol to 5 x 10 ^-1 mol, preferably 1 x 10 ^-2 mol to 5 x 10 ^-1 mol, per mol of silver in the emulsion layer. In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat.
2701197, 2704713, 2728659, 2701197, 2704713, 2728659,
No. 2732300, No. 2735765, No. 2710801, No. 2732300, No. 2735765, No. 2710801, No.
Hydroquinone derivatives described in No. 2816028, British Patent No. 1363921, etc., U.S. Patent No. 3457079,
Gallic acid derivatives described in No. 306926210, etc.
U.S. Patent No. 2735765, U.S. Patent No. 3698909, Special Publication No. 1973-
p-alkoxyphenols described in US Pat. No. 20977 and US Pat. No. 52-6623, US Pat.
No. 3573050, No. 3574627, No. 3764337, JP-A-Sho
Examples include p-oxyphenol derivatives described in No. 52-35633, No. 52-14743, and No. 52-152225, and bisphenols described in U.S. Pat. Examples of methods for introducing the compound of the present invention (color image stabilizer) into the photographic layer of a color photosensitive material include:
It is also possible to dissolve the compound in a low-boiling organic solvent such as ethyl acetate or ethanol and directly add it to a mixed solution of a silver halide emulsion or coupler dispersion without emulsifying it. However, the compound of the present invention (color image stabilizer) is dissolved in a high boiling point solvent such as dibutyl phthalate, tricresyl phosphate, etc. together with the coupler, if necessary in the presence of a low boiling point auxiliary solvent, and is dissolved in an aqueous solution such as gelatin. It is desirable to add it to a silver halide emulsion as an emulsified dispersion in which oil droplets are dispersed in a protective colloid, or as an emulsified dispersion of only the color image stabilizer of the present invention together with a coupler dispersion. Photographic layers to which the compound of the present invention (color image stabilizer) is added include coupler-containing silver halide light-sensitive emulsion layers (e.g., red-sensitive silver halide emulsion layer, edge-sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer). Emulsion layer), non-light-sensitive photographic auxiliary layer (e.g., protective layer, filter layer, intermediate layer, subbing layer, etc.), but in particular, the color image stabilizer of the present invention can be used in a magenta coupler-containing photographic layer. In other words, it is particularly effective for preventing fading and discoloration of magenta images. Typical examples of high-boiling organic solvents used for dispersing the color image stabilizer used in the present invention alone or together with couplers are butyl phthalate, dinonyl phthalate, butyl benzoate, diethylhexyl sebacate, butyl stearate, and dinonyl maleate. , tributyl citrate, tricresyl phosphate, dioctylbutyl phosphate, trihexyl phosphate, triotadecyl phosphate, etc. as described in US Pat. No. 3,676,137, diethyl succinate, dioctyl adipate,
3-Ethylbiphenyl, under the name "Improved Photographic Dye Image Stabilizer", Products, Licensing Index Vol. 83, pp. 26-29 (March 1971).
liquid dye stabilizers listed in Examples of low-boiling organic solvents used as co-solvents along with high-boiling organic solvents include ethyl acetate, butyl acetate, ethyl propionate, ethyl formate, butyl formate, nitroethane, carbon tetrachloride, chloroform, hexane, cyclohexane, ethylene glycol, Examples include acetone, ethanol, dimethylformamide, dioxane, etc., but benzene, toluene, xylene, etc. can also be added to these solvents. Examples of surfactants used in dispersing a solution of the color image stabilizer used in the present invention alone or together with a coupler in an aqueous protective colloid solution include sabonin, sodium alkylsulfosuccinate, and alkylbenzene sulfone. Examples of hydrophilic protective colloids include gelatin (either lime gelatin or acid-treated gelatin), casein, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, Condensate of styrene-maleic anhydride copolymer and polyvinyl alcohol, polyacrylate,
Examples include ethyl cellulose, but the present invention is not limited thereto. The supports used in the present invention are usually cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, and polycarbonate films that are used in photographic materials. , other laminates of these, thin glass films, paper, etc. Paper coated or laminated with baryta or α-olefin polymers, especially polymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene butene copolymers, etc.
Supports such as plastic films whose surfaces are roughened to improve adhesion to other polymeric substances as shown in No. 19068 also give good results. These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. It is also possible to add dyes or pigments to make it colored and transparent. Opaque supports include those that are inherently opaque such as paper, transparent films that have dyes or pigments such as titanium oxide added to them, or those that have been surface-treated by the method described in Japanese Patent Publication No. 19068/1983. It also includes plastic film, and also paper or plastic film that has been made completely light-shielding by adding carbon black, dye, etc. The support is usually provided with an undercoat layer. In order to further improve adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc. When carrying out the present invention, it is of course possible to provide an ultraviolet absorbing layer on the upper surface of the photographic light-sensitive emulsion layer, which is an image forming layer, to be more effective against discoloration and fading caused by light. Yes, it is preferable. Furthermore, the present invention is not limited by the types of commonly used color processing agents, such as color developers, bleaching agents, fixing agents, etc. In particular, the present invention can be advantageously applied to silver-blind color photosensitive materials described in US Pat. No. 3,902,905 and the like. Also West German patent
OLS181390, Japanese Patent Application Publication No. 1972-9728, Special Publication No. 1977-
There are no restrictions on the type of intensifying agent used in the color intensifying treatment described in No. 14625 and the like. Color photosensitive materials to which the present invention can be applied include ordinary color photosensitive materials, especially color photosensitive materials for plants, but also U.S. Pat.
No. 3227551, No. 322552 and US Provisional Publication Patent US,
It may also be a color photographic method, particularly a color diffusion transfer photographic method, as described in No. B351673. In order to obtain a dye image of the color photographic material of the present invention, a color photographic development process is required after exposure. Color photographic processing basically includes color development, bleaching, and fixing steps. In some cases, two steps can be completed in one treatment. Alternatively, a combination of color development, first fixing, and bleach-fixing is also possible. In the development process, a pre-hardening bath, neutralization bath, first development (black and white development), image stabilization bath,
Various processes such as washing with water are combined. Processing temperature is 18℃
More often than not. Especially often used is 20℃
~60°C, and recently especially in the range of 30°C to 60°C. The color developing solution is an alkaline aqueous solution containing an aromatic primary amine color developing agent and having a pH of 8 or more, preferably 9 to 12. Examples of the color developing agent include 4-amino-N,N-diethylaniline, 3
-Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
Methanesulfamide ethylaniline, 4-amino-N,N-dimethylaniline, 4-amino-3-
Methoxy-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, 4-amino-3-methoxy-N
-ethyl-N-β-methoxyethylaniline, 4
-Amino-3-β-methanesulfamide ethyl-
Preferred representative examples include N,N-diethylaniline and salts thereof (eg, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.). In addition, U.S. Patent No. 2193015, U.S. Patent No. 2592364,
JP-A No. 48-649330 or written by LFA Mason,
Photographic Processing Chemistry (Focal
Press-London edition published in 1966), pages 226-229. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. can. Specific examples of antifoggants include potassium bromide, potassium iodide, nitrobenzimidazoles described in U.S. Pat. Tetrazole, US Pat. No. 3,113,864, US Pat. No. 3,342,596, US Pat.
Compounds described in No. 3295976, No. 3615522, No. 3597199, etc., thiosulfonyl compounds described in British Patent No. 972211, or phenazine-N-oxides as described in Japanese Patent Publication No. 46-41675, scientific photographs These include fog suppressants listed in the Handbook, Volume 2, pages 29 to 47. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive couplers may also be used. , a fogging agent such as sodium borohydride, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, and the like. The color photosensitive material of the present invention is subjected to ordinary color development processing, but the following color intensification color development processing can also be applied. For example, US patent
No. 3674490, No. 3761265, West German patent application (OLS)
No. 2056360, Japanese Patent Application Publication No. 47-6338, Japanese Patent Application Publication No. 47-10538
No., JP-A No. 52-13335, No. 52-13324, No. 52-
13336, etc., and West German Patent Application (OLS) No. 2226770, JP-A-Sho.
No. 48-9728, No. 48-9729, JP-A-51-60206,
No. 51-94822, No. 51-133023, No. 52-7728,
52-11037, and the method using a cobalt complex salt, as well as JP-B No. 52-14625 and JP-A-51-
Methods using chlorous acid described in No. 99022, No. 51-103430, etc. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates;
Nitrosophenols and the like can be used.
Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
Various additives can also be added, including the bleaching accelerators described in, for example, No. 8836. The present invention will be explained below based on specific examples, but is not limited thereto. Example 1 10 g of magenta coupler M-1 was dissolved in 20 ml of tricresyl phosphate and 20 ml of ethyl acetate, and this solution was added to 80 g of a gelatin solution containing 8 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate.
It was emulsified and dispersed. Next, this emulsified dispersion was mixed with 145 g (containing 7 g of Ag) of an edge-sensitive silver chlorobromide emulsion (Br 50 mol%), sodium dodecylbenzenesulfonate was added as a coating aid, and a paper support laminated on both sides with polyethylene was added. applied on the body. The coupler application amount was set at 400 mg/m ² . A gelatin protective layer (gelatin 1 g/m ² ) was applied on top of this layer to prepare sample A. When making the above emulsified dispersion using the same method, Table 1
Magenta coupler M-17 or M- as shown in
Combinations of 23 or M-31, the compound of general formula [I] of the present invention, and a comparative compound were prepared. Samples B to T were prepared by adding the compound of general formula [I] and the comparative compound in an amount of 50 mol % based on the coupler used, and coating in the same manner as sample A except for changing the inhibitor. These samples were exposed to light at 1000 lux for 1 second and treated with the following processing solution. Developer Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxyamine sulfate 2g 4-amino-3-methyl-N-ethyl-N-β-
(Methanesulfonamide)ethylaniline・3/
2H ₂ SO ₄・H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make up to 1000ml with water PH6. 8 Processing process Temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fixing solution 33°C 1 minute 30 seconds Washing 28-35°C 3 minutes Each sample with a dye image formed in this way
Attach a Fujifilm ultraviolet absorption filter that cuts out wavelengths below 400 nm and use a xenon tester (irradiation 20
A fading test was carried out for 6 days using 10,000 Lux. Measurements were performed using a Macbeth densitometer RD-514 model (Status AA filter), and changes in concentration at the initial concentration of 2.0 were measured. The results are shown in Table 1.

【table】

[Table] Example 2 Using M-25 as a magenta coupler, a coating composition for the third layer having the composition shown in Table 3 was prepared according to the method for Sample A of Example 1, and a coating composition containing the third layer was prepared. A multilayer sample like No. 3 was prepared. On the other hand, according to the above samples, multilayer samples b to
Five types of f were produced. These samples were exposed and processed in the same manner as in Example 1. The color image of each sample thus obtained was exposed to light using a fluorescent lamp bleacher (15,000 lux) for 4 hours to perform a color fading test, and the change in density of the initial density portion of 1.0 was measured. The results are shown in Table 2. From these results, it was confirmed that the compound of the present invention has a remarkable effect on preventing light browning of color images. In addition, these samples are separately Blue−Green−Red
When three-color separation exposure was applied, the same processing as in Example 1 was performed, and the magenta hues were compared, it was found that samples b to d gave hues with excellent chroma that were exactly the same as sample a. It was found that the addition of the compound of the present invention did not affect the hue in any way.

【table】

【table】

【table】

[Table] Example 3 The magenta coupler in Sample A of Example 1 was replaced with cyan coupler C-1, and the edge-sensitive silver chlorobromide emulsion was replaced with a red-sensitive silver chlorobromide emulsion (Br 50 mol%). Sample g was prepared in the same manner as in Example 1 except for this. A sample in which 50 mol% of the color image stabilizer was added to the coupler was prepared in the same manner. Exposure and development were performed in the same manner as in Example 1. In order to examine the light resistance of each sample that had formed a dye image in this way, we attached a Fujifilm ultraviolet absorption filter that cuts out wavelengths below 400 nm, and after 500 hours of exposure using a xenon tester (illumination intensity of 100,000 lux),
The residual rate of dye after exposure at an initial concentration of 2.0 is expressed as a percentage. In addition, in order to examine heat resistance, the dye residual rate at a nominal concentration of 2.0 when stored in the dark at 100°C for 100 hours was expressed as a percentage.

【table】

[Table] Example 4 The magenta coupler in Sample A of Example 1 was replaced with yellow coupler Y-35, and the edge-sensitive silver chlorobromide emulsion was replaced with a blue-sensitive silver chlorobromide emulsion (Br 80 mol%). Sample 1 was prepared in the same manner as in Example 1 except for the following. A sample in which 50 mol% of the color image stabilizer was added to the coupler was also prepared in the same manner. Exposure and development were performed in the same manner as in Example 1. In order to examine the light resistance, the dye was exposed to light using a xenon tester for 200 hours in the same manner as in Example 3, and the residual rate of the dye after exposure at an initial density of 2.0 was expressed as a percentage. In addition, to test heat resistance, we stored it in the dark at 100℃ for 50 hours.
The dye residual rate at the initial density of 2.0 is expressed as a percentage.
The results are shown in Table 5.

【table】

[Table] From the results of Examples 1 to 4, it can be seen that the compound represented by the general formula [I] of the present invention exhibits a light fastness improving effect superior to that of known antifading agents. Furthermore, it can be seen that it not only improves light fastness but also has an excellent effect of improving heat fastness.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material containing at least one compound represented by the following general formula [I]. [Formula] (In the formula, R and R′ may be the same or different,
hydrogen atom, alkyl group, alkenyl group, respectively.
Aryl group, heterocyclic group, R ₁₁ CO−, R ₁₂ SO ₂ −,
R ₁₃ NHCO- or a silyl group. here
R ₁₁ , R ₁₂ and R ₁₃ each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group,
It represents an alkenoxy group, an aryloxy group, an alkylthio group, an alkenylthio group, an arylthio group, an alkoxycarbonyl group, an alkylcarbonyl group, a hydroxy group, an alkylcarbonyloxy group, a carbamoyl group, or an acylamino group.
R ₇ , R ₈ , R ₉ and R ₁₀ may be the same or different and each represents a hydrogen atom or an alkyl group.
However, among R, R ₁ to _{R 3} , R', and R ₄ to _{R 6} , the groups at mutually ortho positions do not combine to form a ring. )